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After the death of the Empress Elizabeth on January 5, 1762, Charles-Peter succeeded to the throne as Emperor Peter III, and Catherine became empress consort. The imperial couple moved into the new Winter Palace in Saint Petersburg.

The Emperor’s eccentricities and policies, including a great admiration for the Prussian king, Friedrich II, alienated the same groups that Catherine had cultivated. Russia and Prussia had fought each other during the Seven Years’ War (1756–1763), and Russian troops had occupied Berlin in 1761.

Peter, however, supported Friedrich II, eroding much of his support among the nobility. Peter ceased Russian operations against Prussia, and Friedrich suggested the partition of Polish territories with Russia. Peter also intervened in a dispute between his Duchy of Holstein and Denmark over the province of Schleswig (see Count Johann Hartwig Ernst von Bernstorff). As Duke of Holstein-Gottorp, Peter planned war against Denmark, Russia’s traditional ally against Sweden.

In July 1762, barely six months after becoming emperor, Peter lingered in Oranienbaum with his Holstein-born courtiers and relatives, while his wife lived in another palace nearby. On the night of July 8, Catherine was given the news that one of her co-conspirators had been arrested by her estranged husband and that all they had been planning must take place at once.

The next day, she left the palace and departed for the Ismailovsky regiment, where she delivered a speech asking the soldiers to protect her from her husband. Catherine then left with the regiment to go to the Semenovsky Barracks, where the clergy was waiting to ordain her as the sole occupant of the Russian throne.

She had her husband arrested, and forced him to sign a document of abdication, leaving no one to dispute her accession to the throne. On July 17, 1762—eight days after the coup that amazed the outside world and just six months after his accession to the throne—Peter III died at Ropsha, possibly at the hands of Alexei Orlov (younger brother to Grigory Orlov, then a court favourite and a participant in the coup). Peter supposedly was assassinated, but it is unknown how he died. The official cause, after an autopsy, was a severe attack of hemorrhoidal colic and an apoplexy stroke.

At the time of Peter III’s overthrow, other potential rivals for the throne included Ivan VI (1740–1764), who had been confined at Schlüsselburg in Lake Ladoga from the age of six months, and was thought to be insane. Ivan VI was assassinated during an attempt to free him as part of a failed coup: Like Empress Elizabeth before her, Catherine had given strict instructions that Ivan was to be killed in the event of any such attempt. Yelizaveta Alekseyevna Tarakanova (1753–1775) was another potential rival.

Although Catherine did not descend from the Romanov dynasty, her ancestors included members of the Rurik dynasty, which preceded the Romanovs. She succeeded her husband as Empress Regnant, following the precedent established when Catherine I succeeded her husband Peter the Great in 1725.

Historians debate Catherine’s technical status, whether as a regent or as a usurper, tolerable only during the minority of her son, Grand Duke Paul. In the 1770s, a group of nobles connected with Paul, including Nikita Panin, considered a new coup to depose Catherine and transfer the crown to Paul, whose power they envisaged restricting in a kind of constitutional monarchy. Nothing came of this, however, and Catherine reigned until her death.